Excitation-Dependence of Plasmon-Induced Hot Electrons in Gold

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Excitation-Dependence of PlasmonInduced Hot Electrons in Gold Nanoparticles Emanuele Minutella, Florian Schulz, and Holger Lange J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b02043 • Publication Date (Web): 25 Sep 2017 Downloaded from http://pubs.acs.org on September 25, 2017

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The Journal of Physical Chemistry Letters

Excitation-Dependence of Plasmon-Induced Hot Electrons in Gold Nanoparticles Emanuele Minutella,

†Institute

†, ‡

Florian Schulz,

†

and Holger Lange

∗,†,‡

for Physical Chemistry, University of Hamburg, Martin-Luther-King Platz 6, 20146 Hamburg, Germany

‡The

Hamburg Centre For Ultrafast Imaging, CUI, Luruper Chaussee 149, 22761 Hamburg, Germany

E-mail: [email protected]

Abstract The decay of a plasmon leads to a hot electron distribution in metallic nanoparticles. Depending on the processes involved in the excitation, dierent distributions are obtained, which thermalize dierently. We experimentally investigate excitationwavelength and size-dependences on the generation and thermalization of the hotelectrons. We can conrm the absence of size-dependences and we clearly observe two regimes with signicantly dierent relaxation dynamics depending on the photon energy. The hot electron generation is more ecient when exciting with light that enables interband transitions.

1

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Table of Content (TOC) graphic.

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The decay of a gold nanoparticle (AuNP) plasmon results in a hot electron distribution.

18

After photoexcitation, the plasmon dephases within femtoseconds, resulting in a

non-equilibrium electron distribution.

Electron-electron scattering then leads to a ther-

malized, hot distribution within tens of femtoseconds.

These electrons then equilibrate

with their environment within picoseconds by phonon emmision.

7,912

The hot electrons are

considered to be useful for several applications, for example energy conversion, presently intensely discussed in the context of catalysis.

1419

13

and are

A recent study by Wang et

al. highlights the general importance of hot carriers for an enhanced electrocatalysis perfor-

mance.

15

In recent photoinduced oxidative etching experiments hot carriers are important

for the catalytic activity. Following the study by Zhao et al., optical interband transitions more eciently generate hot carriers that then exhibit a higher reactivity as compared to those generated solely by a plasmon decay of energies below the band transition.

14

Recent

theoretical considerations thus aim to unravel the details of the involved processes and their eciency.

9,20,21

Exciting photon energies smaller than the threshold for interband transi-

tions (5d to 6sp) are understood to result in relatively high energetic hot electrons and low energetic holes, whereas photon energies above are expected to result in low energetic hot electrons and holes far away from the Fermi energy. ferent processes are discussed. plasmon itself. Brillouin-zone.

20,21

For the intraband excitation, dif-

The required lattice momentum could be provided by the

Then, the plasmon k -vector is considered to be of comparable size as the

20

A second possible process employs phonons and surface scattering as source

for the lattice momentum.

21

We try to address the involved processes experimentally. We access the initial temperature of the hot electron distribution with transient absorption (TA) spectroscopy. We investigate AuNPs of several characteristic sizes to address size-dependences and we employ excitation wavelengths of the complete visible spectrum in order to dierentiate between inter- and intraband transitions. We can conrm the absence of size-dependences. A clear, binary dependence of the hot-electron relaxation times on the excitation wavelength is observed. The

3



regimes are dened by photon energies above and below the interband transition energy. Interband transitions result in signicantly longer electron-phonon (e-ph) coupling times, stemming from higher initial temperatures. Figure 1a) displays an exemplary TEM image of the AuNPs, synthesised following a modied Turkewich approach,

22

additional details on the synthesis and characterization can be

found in the supporting information. All samples feature a narrow size distribution, which is important to conclude on size-dependency from ensemble measurements.

Steady-state

absorption spectra of the investigated AuNPs are displayed in Figure 1b)

ax

bx AuNPhdiameter: 12nm 23nm 30nm 56nm

AbsorptionhDnormalizedx

1.0 0.8 0.6 0.4 0.2 0.0 400

cx 20

∆AhDmODx

450

500

550

600

650

700

750

WavelengthhDnmx

dx 0.01

13.3 8.85

15

0.00

∆AhDODx

4.45

TimehDpsx

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.00

10

-4.37 5

tmax tmax Th1hps

-8.78 -13.2

0 400

-0.01

tmax Th2hps

-0.02

tmax Th5hps tmax Th10hps

-17.6 500

600

700

400

450

WavelengthhDnmx

500

550

600

650

700

750

WavelengthhDnmx

Figure 1: a) TEM image of 30 nm diameter AuNPs. The scale bar corresponds to 100 nm. b) 2 UVvis spectra of the employed AuNPs. c) TA map of 30 nm AuNPs excited with 100 µJ/cm pulses at 400 nm. d) TA spectra at dierent times after excitation, where

tmax

represents

the time at maximum bleach intensity.

The plasmon absorption depends on the AuNP size.

It shifts to shorter wavelengths

4


Page 5 of 14

and broadens for smaller particles.

23,24

The increased electron temperature after photoexci-

tation can be investigated using a TA pump-probe experiment.

25

The pump pulse excites

the AuNPs which results in a hot-electron distribution. An increased electron temperature changes the occupation of the electronic states near the Fermi level. This changes the dielectric constants and therefore the extinction coecient which leads to a broadened plasmon absorption.

26,27

The dierential change in absorption is the contrast in the TA experiment

and is directly related to the increase in electron temperature.

11

The signal constitutes of a

negative absorption change (bleach) at around 525 nm with two positive sidebands. When the electrons cool down, the resonance narrows and the TA contrast vanishes. Figure 1c) displays an exemplary TA map of 30 nm diameter AuNPs. Horizontal cuts through the TA map lead to dierential absorption spectra at xed times, as displayed in Figure 1d) for selected times after photoexcitation. The spectra can be tted with Gaussian functions in order to extract the quantitative absorption change (see supporting information for details on the data analysis).

Monitoring the absorption change for dierent pump-probe delays

allows to follow the electron cooling.

Figure 2 shows the normalized bleach change after

photoexcitation for dierent AuNPs. Additional plots with dierent excitation wavelengths are shown in the supporting information. D ia m e te r / p u m p in te n s ity :

1 .0

B le a c h in te n s ity ( n o r m .)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1 2 n 2 3 n 3 0 n 5 6 n 3 0 n 3 0 n

0 .8

0 .6

m

m

m

m

m

m

/ 1 0 / 1 0 / 1 0 / 1 0 / 2 0 / 3 0

0 µ J 0 µ J 0 µ J 0 µ J 0 µ J 0 µ J

/c m /c m /c m /c m /c m /c m

2 2 2 2 2 2

0 .4

0 .2

0 .0 0

2

4

6

8

T im e ( p s ) Figure 2: Temporal evolution of the bleach intensity of dierent-sized AuNPs excited with 650 nm and dierent pulse intensities.

5



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The relaxation dynamics include two components, which can be described by a biexponetial decay. The fast component is related to the e-ph coupling, while the slow component describes the coupling to the environment.

Comparing dierent AuNPs at xed

excitation conditions reveals no size-dependences which conrms earlier studies.

12,26,2830

As

a possible explanation for the absence of a size-dependence Hodak et al. suggested an inuence of grain boundaries in the AuNPs that could lead to additional scattering events which shorten the decay time.

12

But not just a dierence in the decay mechanism could lead to a

dierent decay time, also the excitation mechanism could play an important role. Bernadi et al. account the plasmon itself for delivering the necessary k-momentum for the intraband

transition.

20

This process would be size-independent.

In contrast, Brown et al.

recently

reported a size-dependence for the excitation of hot electrons below the interband threshold in a size range from 10 to 40 nm due to surface scattering eects.

21

Our observations support

the sole plasmon concept. In Figure 2, the slopes of bleach relaxation decrease for increased excitation intensity, indicating a slower relaxation. Increasing the pump intensity increases the amount of initial high-energy electrons and the temperature after electron-electron scattering. The electron heat capacity increases linear with temperature, while the e-ph coupling strength does not. This results in a linear relation of initial temperature and e-ph coupling time. Consequently, the electron temperature and accordingly the measured signal decays more slowly at higher pump powers.

9,21,25,31

Thus, the e-ph coupling time is a suitable direct

measure for the initial electron temperature and it does not depend on the concentration or other experimental parameters such as for example integration times.

25

That is why we make

use of the e-ph coupling time for the systematic investigation of the hot-electron generation. Experiments with dierent excitation wavelengths at xed excitation intensities allow to study the excitation mechanism.

Figure 3 displays the normalized bleach relaxation for

dierent AuNPs sizes pumped with excitation wavelengths covering the visible spectrum. A wavelength-dependence is apparent. We observe the splitting of the relaxation curves into two regimes. This is most obvious for AuNPs of 12 nm and of 30 nm diameter. Samples

6


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a

b )

)

1 .0

P u m p w a v e le n g th :

1 .0

1 2 n m

0 .8



4 0 0 n m

0 .6

0 .4

4 2 5 n m

2 3 n m

0 .8

4 5 0 n m 4 7 5 n m 5 0 0 n m

0 .6

5 5 0 n m 5 7 5 n m

0 .4

6 0 0 n m 6 2 5 n m

0 .2

0 .2

0 .0

0 .0

6 5 0 n m 6 7 5 n m

0

2

4

6

8

7 0 0 n m

1 0

0

2

4

T im e ( p s )

c

6

8

1 0

8

1 0

T im e ( p s )

d )

)

1 .0

1 .0

3 0 n m

0 .8



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0 .6

0 .4

0 .2

5 6 n m

0 .8

0 .6

0 .4

0 .2

0 .0

0 .0 0

2

4

6

8

1 0

0

T im e ( p s )

Figure 3:

2

4

6

T im e ( p s )

The bleach intensity for dierent sized AuNPs (a)12nm, b)23nm, c)30nm and

d)56nm) excited with dierent wavelengths. For all measurements the pump intensity was 2 kept constant at 100 µJ/cm .

7



pumped with wavelengths shorter than 550 nm (photon energies of 2.25 eV) show a common slow relaxation, longer wavelengths result in a faster relaxation. The dependency of the maximum bleach intensity is similar, but scatters more (see supporting information gure S3). Figure 4 displays the extracted e-ph coupling times corresponding to the relaxation curves in Figure 3. The e-ph coupling times show no clear wavelength-dependence, but a clustering into two regimes. Within the regimes, in addition to the absence of wavelength-dependences, no size-dependences are apparent. The regime with the longer relaxation time is in the spectral range from 400 nm to 550 nm. There, direct interband transitions from the 5d to the 6sp band are possible,

20,3235

which are expected to be favored over intraband transitions.

20,21

We clearly see their impact, but in contrast to the theoretical study of Brown et al., we observe a separation of the dynamics either with or without interband transitions and no smooth change spanning over several tenths of eV.

21

A u N P d 1 2 2 3 3 0 5 6

2 .5

e - p h c o u p lin g tim e ( p s )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 14

ia m e te r : n m n m n m n m

2 .0

1 .5

1 .0

4 0 0

4 5 0

5 0 0

5 5 0

6 0 0

6 5 0

7 0 0

P u m p w a v e le n g th ( n m ) Figure 4: Extracted e-ph coupling times for dierent-sized AuNPs. The two e-ph couping time regimes are indicated by red boxes.

Pump-intensity dependent experiments allow to further explore the eciency of the hotelectron generation following intraband and interband excitation.

As no size-dependences

were observed earlier, we focus on a single size, 30 nm diameter AuNPs. Figure 5a) shows pump intensity-dependent studies with selected representative wavelengths from the regimes that allow interband transitions and that do not allow interband transitions. Extrapolating

8


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a)

b)

3.0

0.016

2.5 2.0 Pumpswavelength: 415snm 425snm 450snm 500snm 575snm 625snm 650snm 700snm

1.5 1.0 0.5 0

100

200

300

Slopes(psscm2 µJ-1)

0.014 e-phscouplingstimes(ps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.012 0.010 0.008 0.006 0.004 0.002 400 450 500 550 600 650 700

400

Pumpsintensitys(µJ/cm2) Figure 5:

Pumpswavelengths(nm)

e-ph coupling times of 30 m AuNPs excited with dierent, xed wavelengths.

The solid lines are linear ts. b) Slopes of the dependences observed in a). The red boxes highlight the two relevant regimes.

the e-ph coupling times to zero intensity yields

0 ≈ 0.9 ps τel−ph

for the internal e-ph coupling

time. Despite the fact that this method of determining the internal e-ph time is not very accurate to measure small dierences,

11

most of the curves intercept at same point. Based on

this we conclude that the decay process is not dierent if interband transitions were possible during the excitation. No additional process like electron-hole recombination seems to be involved, because otherwise an oset would occur. Starting from the intercept, as expected, we observe a linear increase of the e-ph coupling time with increasing excitation intensity. This is due to a linear increase of the initial electron temperature with absorbed optical energy. The slopes of the e-ph coupling time to pump intensity curves also cluster into two regimes, separated by the interband transition energy. The slopes are summarized in Figure 5b) and dier be a factor of approximately two. When above the interband transition energy, the same excitation intensity can much more eectively generate hot electrons. In conclusion, we observed that optical excitation allowing interband transitions in AuNPs more eectively generates hot electrons than that solely allowing plasmonic excitations. Aside from the related transition, no wavelength-dependences are observed. Size-dependences are also absent, supporting the concept of the generation of intraband hot electrons by the

9



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plasmon providing the necessary k-momentum. Surface scattering seems to be less relevant in the investigated size range. Nevertheless, for very small particles such eects can become more important.

In scope of the importance of hot electrons for photocatalytic reactions

and photovoltaics, our observations reveal that the possibility of interband transitions is an important factor that has to be taken into account. Subsequent studies should address the yield of catalytic reactions for dierent wavelengths. In TA experiments, only thermalized hot electrons are probed.

Ultrafast UV photoelectron spectroscopy studies could address

the non-equilibrium electron distributions.

36

The understanding of the initial distribution

depending on the excitation conditions could allow to clarify the details of the plasmon decay, signicant for advancing this eld of plasmonics.

Acknowledgement We acknowledge nancial support from the German Research Foundation (DFG) via the Cluster of Excellence The Hamburg Centre for Ultrafast Imaging (CUI). F.S. is supported by the DFG via the project SCHU 3019/2-1.

Supporting Information Available Details on synthesis and characterization of AuNPs, experimental procedures, details about analysis and tting procedure, and supporting results. This material is available free of charge via the Internet at

http://pubs.acs.org/ .

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Excitation-Dependence of Plasmon-Induced Hot Electrons in Gold

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